Design and Development of Room Temperature Carbonylation

室温羰基化反应的设计与开发

• 批准号: 03453103
• 负责人: MURAI Shinji
• 金额: $ 4.42万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453103/
• 关键词: Catalyst; Silylcobalt; Acetal; Lactone; Cobalt carbonyl; Hydrosilane; Carbon monoxide; シロキシメチル化; コバルト; 常圧カルボニル化; カルボニル化

The objective of this research is to establish a guiding principle of developing catalytic systems that enable room temperature carbonylation. The strategy we took was to utilize two different metal centers in a molecular catalyst, one to activate a reaction site in a substrate, the other to effect carbonylation.Thus accumulated knowledge had lead to suggest the advantage of the use of silylcobalt as the catalyst for this purpose. For example, a silylcobalt carbonyl complex reacted with an oxygen-containing substrate and cleaved its carbon-oxygen single or double bond to result in the formation of an intermediate having a carbon-cobalt bond, the latter being essential for carbonylation to take place, Along with this line, a couple of entirely new catalytic reaction of oxygen-containing compounds such as acetals, lactones, and aromatic aldehydes with carbon monoxide and hydrosilanes have been developed. The stereochemical aspects of these new reactions have been clarified. It is expected that these results will make significant contribution to the fields of designing new catalyst system and synthetic organic chemistry.

这项研究的目的是建立一个指导原理，以开发催化系统，以实现室温羰基化。我们采取的策略是利用分子催化剂中的两个不同的金属中心，一种是激活底物中的反应位点，另一种是对羰基化的影响。因此，积累的知识导致了使用silylcobalt作为此目的的催化剂的优势。例如，一种甲硅烷基核心的羰基复合物与含氧底物反应并裂解其碳 - 氧单或双键以导致形成具有碳粘结键的中间体，后者对于羰基是至关重要已经开发了用一氧化碳和氢烷醛的醛。这些新反应的立体化学方面已经阐明。预计这些结果将为设计新的催化剂系统和合成有机化学的领域做出重大贡献。

项目成果

N.Chatani, T.Murai, T.Ikeda, T.Sano, Y.Kajikawa, K.Ohe, S.Murai: "Stereochenical Aspects of Catalytic Siloxymethylation of Various Oxygen-Containing Compounds with Hydrosilanes and Carbon Monoxide in the Presence of Dicobalt Octacarbonyl" Tetrahedron. 48.

N.Chatani、T.Murai、T.Ikeda、T.Sano、Y.Kajikawa、K.Ohe、S.Murai：“在二钴存在下，各种含氧化合物与氢硅烷和一氧化碳催化硅氧基甲基化的立体化学方面

村井 真二: "Co_2(CO)_8-Catalyzed Reaction of Aromatic Aldehydes with Hydrosilanes and Carbon Monoxide"

Shinji Murai：“Co_2(CO)_8 催化芳香醛与氢硅烷和一氧化碳的反应”

S.Murai: "CO_2(CO)_8-Catalyzed Reaction of Acetals and Lactones with Hydrosilanes and Carbon Monoxide"

S.Murai：“CO_2(CO)_8-催化缩醛和内酯与氢硅烷和一氧化碳的反应”

村井 真二: "Co_2(CO)_8-Catalyzed Reaction of Acetals and Lactones with Hydrosilanes and Carbon Monoxide"

Shinji Murai：“Co_2(CO)_8 催化的缩醛和内酯与氢硅烷和一氧化碳的反应”

村井 真二: "Stereochemical Aspects of Catalytic Siloxymethylation of Various Oxygen-Containing Compounds with Hydrosilanes and Carbon Monoxide in the Presenu of Dicobalt Octacarbonyl" Tetrahedron. 48. 2013-2024 (1992)

Shinji Murai：“八羰基二钴中各种含氧化合物与氢硅烷和一氧化碳的催化硅氧基甲基化的立体化学方面”四面体。2013-2024 (1992)